New copolymers



Unite States NEW COPOLYMERS Herbert K. Wiese, Cranford, and Winthrope C. Smith,

Westfield, N. J., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application August 17, 1954 Serial No. 450,540

27 Claims. (Cl. 260-821) tetrachloride at a temperature of 25 C. to +100 C.

These compounds have the following general formula:

where R represents hydrogen substituents, usually methyl or other alkyl groups.

It has now been found that these cyclodienyl trichlorosilanes can be polymerized with 50-90% by weight of atent 2,833,748 Patented May 6, 1958 freezing points below C., the hydrocarbons which have freezing points below 0 C., and a considerable number of mixed solvents.

various unsaturated hydrocarbons, e. g. vinyl aromatics,

such as styrene and its analogs, diolefins such as butadiene, isoprene, and olefins such as isobutylene, etc., alone or in combination. The reaction is carried out at temperatures ranging from 10 C. down to 164 C. by the appli cation to the cold feed of a Friedel-Crafts type catalyst,

preferably in solution in a low-freezing non-complex form-- ing solvent.

For the catalyst, any of the catalysts disclosed by N. O. Calloway in his article on The Friedel-Crafts Synthesis printed in the issue of Chemical Reviews, published for the American Chemical Society at Baltimore, in 1935, in volume XVII, No. 3, the article beginning on page 327, the list being particularly well sh'oiwnon page 375, may be used. It may be noted that while most of these catalysts are solids, a limited number are fluids including boron trifluoride which is a gas, and titanium tetrachloride which is a liquid. The fluid catalysts may be used directly as such or diluted for reaction control. The solid catalysts are preferably dissolved in an appropriate solvent.

For the solvent, any material which will dissolve a substantial amount, preferably more than approximately 0.1% of the Friedel-Crafts catalyst, has a freezing point below 0 0, thereby being low-freezing, and will boil away from the dissolved catalyst substance with a rise in temperature above the normal boiling point of the solvent of no more than 1 or 2 degrees, thereby being non-complex forming, is satisfactory. The preferred catalyst solvents are such substances as ethyl or methyl chloride, ethylene dichloride, chloroform, carbon disulfide, ethylidene fluoride, liquid ethylene, liquid ethane, liquid propane, liquid butane, and the like. These solvents are representative of a wide range of other substances, includas t e saqe P l has aliphatis 9 m a n The advantages of the invention will be better understood from a consideration of the following experimental data which are given for the sake of illustration, but without intention of limiting the invention thereto.

Exampie 1.A charge of 150 cc. CH Cl at 60 C. and 2 g. cyclopentadienyl trichlorosilane and 20 g. isobutylene was made to a 3-inch diameter reactor. This was chilled and maintained at C. by external ethylene refrigeration. To this was added continuously with agitation over 6 minutes 50 cc. of a catalyst solution of 0.1 g. AlCl3 dissolved in 100 cc. CH Cl (at 60 (3.). Polymer formed rapidly in a coarse slurry fouling only at the liquid interface near the end of the reaction. Then 3 cc. of a 1.17 g. AlCl in 100 cc. CH Cl concentrate was added effecting no further reaction indicating a catalyst efficiency of -440 g./ g. assuming 100% conversion. The polymer was quenched and washed in isopropyl alcohol. It was not hot milled to avoid possible hydrolysis and condensation of unreacted cyclopentadienyl trichlorosilane. A 10 g. sample of this high molecular weight, tough polymer was squeezed to remove excess alcohol and dissolved in 600 cc. of cyclohexane. It was precipitated with acetone and the clear supernatant liquid discarded. This was repeated two more times to rid the polymer of unreacted cyclopentadienyl trichlorosilane. The silicon analysis showed 0.21 and 0.18 wt. percent Si in duplicate tests. This, calculated on the basis of the trichlorosilane form in the polymer, indicates 1.42 wt. percent cyclopentadienyl trichlorosilane in the polymer compared with 9.09 wt. percent cyclopentadienyl trichlorosilane in the feed. This gives a 15.5% utilization and a rough partition coelficient (on) of 0.155. This polymer on standing at room temperature crosslinked to 100% insoluble (CCL benzene, cyclohexane) polymer. Molecular weight and unsaturation could not be obtained.

Example 2.-Another series of polymers were made in a similar fashion employing 10, 20, 40 wt. percent cyclopentadienyl trichlorosilane on the isobutyl'ene and 5/1 dilution with CHgCl.

These polymers were prepared for evaluation by quenching and washing in absolute methyl alcohol to avoid hydrolysis cross linking and purified by a threefold precipitation from cyclohexane with dry acetone and,

vacuum dried at 70 C. and stored in a desiccator over CaCl The unsaturation figures do not show changes in amount of cyclopentadienyl trichlorosilane in the polymer but "the polymers of Example 110% cycle pentadienyl trichlorosilane in the feed and Example 2-283 at 20 and 40% cyclopentadienyl trichlorosilane in the feed show a regular progression of increasing silicon content which correlates with the cyclopentadienyl trichlorosilane in the feed stock.

Portions of these polymers were compounded in the following formulations and cured 60 minutes at 307 F.

also prepared as follows:

Parts by wt. Butyl rubber 100 Carbon black t 30' Zinc oxide Coray 230 Oil 5 Sulfur 2 Tetramethyl thiuram disulfide 1 Z-mercapto-benzo-thiazole 1 These ingredients were made up in a cement of 20% by weight of solidsin hexane. 4

Test pieces of glass plate and pieces of glass filter cloth (100 mils thick) were washed carefully with n'aphtha and dried. These were coated four times each with the trichlorosilane copolymer cement with 'a half-hour drying period after each coat and rolled tog'ethe'r. Other test pieces of plate'and fabric were coated twice; each with the control cement (higher solids content) and dried and rolled together in the same fashion.- These structures were laced in an -air oven'for one hour at-300 F-.,-cooled and tested for adhesion ona Scott tester at 2 in. per minute. The results were asronows:

, Adhesion, Structure #llllllmlalar Separation c Pulled .fibers' from fabric.

having the general formula 7. Us? P. hydrogen and alkyl and aft utisa tui'atd hydrocarb 4. 2. A solid copolymer of a cyclodienyl trichlorosilane having the' formula OH:CHCH:CHC(H)-Si0la and an unsaturated hydrocarbon selected from the class consisting of vinyl aromatics, diolefins and olefins.

3. A solid copolymer of a cyclodienyl trichlorosilane having the general formula in which "R is selected from the group consisting of hydrogen and alkyl and a vinyl aromatic.

4. A solid copolymer of a cyclodienyl trichlorosilane having the general formula CR:CROR:CRC(R)SiCla in which R is selected from the group consisting of hydrogen and alkyl and styrene.

5. A solid copolymer of a cyclodienyl trichlorosilane having the general formula in which R is selected from the group consisting of hydrogen and alkyl and a diolefin.

6. A solid copolymer of ,a cyclodienyl trichlorosilane having the general formula in which R is selected from the group consisting of hydrogen and alkyl and butadiene.

7. A solid copolymer of a cyclodienyl trichlorosilane having the general formula o'monomoacau-sxox;

in which R is selected from the group consisting of hydrogen and alkyl and isobutylene.

9. A solid copolymer of a cyclopentadienyl trichlorosilane having the formula and isobutylene.

10. A process which comprises copolymerizing a mixture of a-cyclodienyl trichlorosilane having the general formula in which R is selected from the group consisting of hydrogen and alkyl and an unsaturated hydrocarbon in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between -l0 and -164 C. V

11. A process which comprises copolymerizing a mixture of 'a cyclodienyl trichlorosilane having the formula and an unsaturated hydrocarbon, selected from the' group consisting of Vinyl aromatics, diolefins and olefins, in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between -10 and -l64 C.

12. "A process whin camrises eep-ol 'meuzing a ture of a cyclodienyl trichlorosilane having the general formula CR:CRCB:CRC(R)SiCls in which R is selected from the group consisting of hydrogen and alkyl and a vinyl aromatic in the presence of a Friedel-Crafts type catalyst dissolved in a noncomplex forming, low freezing solvent at a temperature between 10 and l64 C.

13. A process which comprises copolymerizing a mixture of a cyclodienyl trichlorosilane having the formula CH:CHCH:CHC (H)SiCIs and styrene in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freez-.

ing solvent at a temperature between 10 and 164 C. 14. A process which comprises copolymerizing a mixture of a cyclodienyl trichlorosilane having the general formula cR=oRcR=oRc R -sicn and butadiene in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between -10 and 164 C.

16. A process which comprises copolymerizing a mixture of a cyclodienyl trichlorosilane having the formula and isoprene in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between 10, and -164 C. 17. A process which comprises copolymerizing a mixture of a cyclodienyl trichlorosilane having the general formula omonomonmm-stoa in which R is selected from the group consisting of hydrogen and alkyl and isobutylene in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between l and -164 C.

18. A process which comprises copolymerizing a mixture of cyclopentadienyl trichlorosilane having the formula and isobutylene in the presence of aluminum chloride catalyst dissolved in methyl chloride at a temperature between -10 and 164 C.

19. A solid copolymer of a cyclopentadienyl trichlorosilane having the formula and an olefin.

20. A high molecular weight tough solid copolymer of about 1.4 to 5.9% of combined cyclopentadienyl trichlorosilane having the formula CH:CHCH:CHC (ED-S101:

and about 98.6 to 94.1% of combined isobutylene.

21. Product according to claim 20 having a Staudinger molecular weight of about 98,000 to 128,000 and an iodine number of about 2.74 to 3.47.

22. Composition comprising about 100 parts by weight of the product defined in claim 21, and about 30 to 50 parts by weight of carbon black.

23. Composition according to claim 22, cured by heatmg.

24. A process which comprises copolymerizing a mixture of about 10 to 50 parts by weight of a cyclopentadienyl trichlorosilane having the formula CH:GHCH:CHC (ED-SiCla and about 50 to by weight of an olefin, in the presence of a Friedel-Crafts type catalyst dissolved in a non-complex forming, low freezing solvent at a temperature between -10 and -164 C.

25. A process which comprises copolymerizing a mixture of about 10 to 40% by weight of a cyclopentadienyl trichlorosilane having the formula CH: CHGH: CH? (ED-Sic]:

and about 90 to 60% by weight of isobutylene in the presence of methyl chloride as diluent, and in the presence of a catalyst comprising aluminum chloride dissolved in methyl chloride, at a temperature of about C., to producea tough copolymer having a Staudinger molecular Weight of about 98,000 to 128,000, and containing about 1.4 to 5.9% of combined cyclopentadienyl trichloro silane.

26. Process according to claim 25 followed by compounding about 100 parts by weight of the resulting cclaptilymer with about 30 to 50 parts by weight of carbon b ac 27. Process according to claim 26 followed by curing the resulting composition by heating.

References Cited in the file of this patent OTHER REFERENCES Mark et al.: Physical Chemistry of High Polymeric Systems, Interscience, 1950, pp. 454-456.

Martin Jan. 26, 1954 

1. A SOLID COPOLYMER OF A CYCLODIENYL TRICHLOROSILANE HAVING THE GENERAL FORMULA 